Process for the dyeing of polyacrylonitrile fibers



United States Patent Office 3,355,243 PROCESS FOR THE DYEING FPOLYACRYLO- NITRILE FIBERS Jakob Bindler, Riehen, and Emanuel Durr,Arlesheim,

Basel-Land, Switzerland, assignors to J..R. Geigy, A.G.,

Basel, Switzerland N0 Drawing. Filed June 8, 1964,.Ser. No. 374,233Claims pri0rity, application Switzerland, June 11, 1963, 7,284/63 19Claims. (Cl. 8-55) The present invention concerns a process to attainlevel dyeings on copolymeric acrylonitrile and especially on acrylicfibers having color saturation values in the range from about 2.5 to6.5, the dye liquors used therefor as well as, as industrial product,the uniformly dyed material.

Hitherto, in order to dye polymeric or copolymeric acrynonit'rile by theexhaustion method with basic dyestuffs and in level shades, a dye liquorhas been used which, in addition to basic dyestuffs, contained as dyeassistants tertiary, monoor bis-quaternary organic nitrogen compoundshaving at least one higher alkyl radical per molecule. As a rule, theseassistants detrirnentally affect the fastness to light of the dyeingsobtained and block the fibers, i.e. as soon as a portion thereof hasbeen drawn onto the fiber, they reduce the absorption power of thevfiber both for further basic dyestuff and for further dye assistant.This blocking effect on the fiber makes the re dyeing and in particularthe cross dyeing of a shade already attained very much more difficult.Since the blocking effect caused by the known dye assistants on thepolyacrylonitrile fiber affects the individual basic dyestuffs present,for instance, in a conventional mixed dye in different degrees, it isalso generally impossible to attain or reproduce a desired shade withusually preferred mixtures of 'basic dyestuffs. Finally the blockingeffect has a varying influence on'the rate at which the basic dyestuffsdraw onto the aforesaid type of fibers which, in practice, easily leadsto uneven distribution of the dyestulf. Moreover, since the hithertoused dye assistants which have drawn onto the fiber are. very diflicultto remove, this blocking effect is generally irreversible.

' It has now been found that polymeric, and especially copolymericacrylonitrile fibers can be dyed in level shades while avoiding theabove disadvantages by dyeing these materials in anacid, preferablyorganic acid and more particularly an acetic acid, dyebath whichcontains the basic dyestuffs and a polyamine, which latter has three ormore, preferably 3 to quaternized basic nitrogen atoms, a polyglycolether chain and at least one lipophilic substituent, whereafter thedyeing process is completed in known manner.

The polyamines usable in the dyeing treatment accordingto the inventionare, in. particular, polyalkylene polyamine compounds the alkylenecomponents of which are :preferably of from 2 to 3 carbon atoms each,e.g. 1,2-

ethylene, or 1,2- or 1,3-propylene radicals; the number ofamino-nitrogens in these amines ranges from 3 to 5 and is preferably 3;forexample, diethylenetriamine, tri- 3,355,243 Patented Nov. 28, 1967ethylenetetramine, tetraethylenepentamine or dipropylenetriamine arecompounds from which the polyamines usable according to the inventionare derived. The latter polyamines further contain as lipophilicsubstituent an 5 alkyl or alkenyl radical having, particularly, 14 to 20carbon atoms. Examples of such radicals are the tetradecyl, hexadecyl,octadecyl or eicosyl or the oleyl radical. The polyglycol ether chain ofthe polyamines usable according to the invention has about 10 to 50, andpreferably from 15 to 20 alkyleneoxy groups; these are mainly ethyleneoxy groups and there may be present in the chain a minor portion,preferably from one to two individual propyleneoXy or styreneoxy groups.

These polyamines are obtained by adding the desired alkylene oxidecomponent and if desired also minor amounts of styrene oxide to thepolyamine having at least one lipophilic radical and three or morenitrogen atoms. The addition products thus obtained are then quaternizedto form the product to be used according to the invention with an esterderived from a low aliphatic or araliphatic alcohol and a strong acid,e.g. with dimethyl or diethyl sulfate, ethyl chloride or ethyl bromide,or benzyl chloride, arylsulfonic acid alkyl esters such as p-toluenesulfonic acid methyl or ethyl ester, chloroacetic or bromoacetic acidmethyl or ethyl ester or chloropropionic or bromopropionic acid methylor ethyl ester.

For instance, N octadecyl diethylenetriamine condensed with ethyleneoxide and permethylated with dimethyl sulfate to a product containing apolyglycol ether chain having 15 to 2'0 ethyleneoxy groups has anexcellent levelling action.

The basic dyestuffs used according to the invention are advantageouslyof the following dyestuif classes: thiazines, oxazines,diphenylmethanes, triphenylmethanes,

" rhodamines, azo, anthraquinone dyestuffs and, preferably,

monoazo, methine and azamethine dyestuffs, which all contain oniumgroups, the onium groups being mainly ammonium groups.

As copolymeric acrylonitrile fibers, those fiber materials are used, thefiber-forming substance of which consists of a synthetic long-chainpolymer comprising at least by weight of acrylonitrile and which possesssuflicient dyesites to impart to the fibers a color saturation valueabove 2, and especially in the range of about 2.5 to 6.5. The acidgroups of copolymer effecting the afiinity of the dyestulf are mainlythe carboxylic acid, carboxylic acid amide or hydroxy groups as well asthe sulfonic acid group.

The balance is essentially derived from vinylpyridines and othermonomers copolymerizable with acrylonitrile which are described, forinstance, in Canadian Patent 557,597, issued May 20, 1958.

Suitable acrylic fibers which satisfy the above require- 3 the inventionwhen mixed with other fibers, e.g. with cellulose or polyamide fibers,in particular, however, with wool.

These fibers are dyed by the exhaustion process from short, concentrateddye baths (goods-to-liquor ratio of 1:5) as well as from long dye baths(goods-to-liquor ratio of 1:100) at a temperature of preferably 60 to100 C. The finished fibers are then rinsed and dried.

Depending on the depth of shade desired, the dosage of the aforesaidpolyamine dye assistant in the dye bath ranges between 1 and 2%calculated on the weight of the goods. Deep dyeings require lesslevelling agent than light shades.

The acid reaction of the liquor is preferably adjusted by addition oforganic acid, in particular formic acid, acetic acid or tartaric acid.For instance, to secure pH- values of the dye bath of preferably 3.5 to5, 80%-acetic acid is added in amounts of 2 to and in particular 4 to6%, calculated on the weight of the goods to be dyed in the bath. Thedyeings obtained according to the invention on the above described typesof acrylic fiber materials are very level and fast to light. They caneasily be re-dyed or cross-dyed.

The inventive process for dyeing polymeric and especially copolymericacrylonitrile fibers has among others the following advantages oversimilar known processes: It does not block the fibers; it affords abetter dyestuif yield, especially in deeper shades; an overdosage of thepolyamine used according to the invention does not decrease the dyestuifyield; the process permits an easy crossdyeing of light shaded parts todeeper shades and does not adversely influence the fastness of dyeingsobtained with basic dyestuffs.

The color saturation value mentioned in this specification and in theappended claims is the theoretical saturation value of usable acrylicfibers with a basic dyestuff of average afiinity for such fibers,expressed in grams of dyestuff per 100 grams of fiber (viz, Surean,Progrs raliss dans la teinture des fibres Acryliques, Teintex, June1961).

The following non-limitative examples illustrate the invention. Thetemperatures are given therein in degrees centigrade. C.I. means ColourIndex, Second Edition, 1956, published by The Society of Dyers andColourists, Bradford, England and The American Association of TextileChemists and Colorists, Lowell, Mass, USA.

4 liquor (liquor ratio 1:50) which contains 0.7% of C.I. Basic Yellow19, i.e. dyestuff of the formula onto 0.3% of C.I. Basic Red 22, i.e.dyestuff of the formula LHa and 2% of C.I. Basic Blue 41, i.e. dyestulfof the formula as Well as 5% of acetic acid (100%), 10% of sodiumsulfate and 2% of the condensation product of 15 to 20 equivalents ofethylene oxide with N-octadecyl diethylenetriamine, quaternized withdimethyl sulfate, all percentages being calculated on the weight of thefibers. The liquor is heated to 80 within 10 minutes and then thetemperature is raised at the rate of half a degree centigrade per minuteto the boil. The material is left in the liquor for 2 hours at thistemperature and then the liquor is allowed to cool to within 30 minutes.The material so dyed is then taken out of the dyebath, and rinsed firstwith lukewarm and then with cold water.

The hanks of polyacrylonitrile are dyed a very level grey color, andhave good fastness to light. The dyeings can easily be cross-dyed.

When the condensation product of 15 to 20 equivalents of ethylene oxidewith N-octadecyl diethylenetriamine quaternized with dimethyl sulfate isreplaced in the above example by corresponding amounts of the dyeassistants listed in Table I below and otherwise the procedure describedin the above example is followed, then dyeings having similarly goodproperties are obtained.

TABLE I Dye assistant condensation product of X mol of ethylene oxidewith 1 mol of polyamine, quaternized No.

X Alkylene oxide Polyamine Quaternizing agent Ethylene oxide 1540 pluspropylene Dimethyl sulfate.

oxide. 15-20 Ethylene oxide Diethyl sulfate. 15-20 do Benzyl chloride.15-20 do Toluene sulfonic acid methyl ester.

20 do 0 Dimethyl sulfate. 12 do N-oleyl-triethylenetetramine Do. doN-hexadecyl-tetraethylenepentamine Do. 15-20 doN-octadeeyl-dipropylenetriamine Do. 18 20 Ethylene oxide plus styreneN-octadecyl-diethylenetriamme Do. oxide.

When the same rocedure as in Exam le 1 is followed EXAMPLE 1 P P but,instead of the, in all, 3% of the dyestuif mixture given in Example 1,corresponding parts of the dyestuffs listed in Column 11 of Table II areused, then dyeings of the shades given in Column HI of that table areobtained, which have similar satisfactory properties.

-T.ABLE H I 11 III N o. Dyes'tufi Shade on polyacrylonitrile fibers 110.1. Basic Blue 49 Blue.

12 0.1. Basic Red 14 Red.

/CHCHzCl LOMF N s f CH C a H3 13 0.1. Basic Yellow 13 Yellow.

a... s 14 0.1. Basic Green 1 (42040) Green.

15. Deorlin Light Yellow 4RL Yellow.

(CH3) aN-CHr-O ON=N-'|C 16..." Deorlin Light Blue BL Blue.

P o NNI s0.cm-

CH; e I

NH- -0 cmcmmcmm 17 0.1. Basic Blue 5 (42140).. Do.

18..... 0.1. Basic Blue 44 Do.

I O NH:

CH3 804-0 13 Y el/ "5 o fNH -a-e0 GZEhCHiN' CH2 A 19; L 0.1. BasieBluezl. 42025 Do.

.20... 1051. Basic" Green16 Olive.

(GEM-1 (0301-! TABLE IICnt7lnued I II 111 i No. Dyestufi Shade onpolyacrylonltrile fibers 21 C.I. Basie Orange 21 (48035) Orange. I

22 C.I. Basie Orange 22 (48040) D0.

23.... 0.1. B11510 Red 13 (48015) Pink.

24-- C.I. Basic Violet 7 (48020) Red-violet.

25 C.I. Basie Violet 20 Blue-violet.

CH;N=C O 01H;

OHaSOa 26. C.I. Basie Violet 21 Violet.

CH; omoo o-oH=oH-N-oomom o1- H: N

27. C.I. Basie Yellow 12 (48065) Yellow.

28. C.I. Basic Yellow 20 D0.

C H: JCH;

CCH=CH--HN- OCH: Cl 69/ I? CHzO CH;

29 0.1. 48013 Q. Pink.

30. C.I. B8510 Blue 6 (51175) Blue.

31. 0.1. Basic Yellow 3 (41005) Yellow.

32. C.I. Basie Green 4 (42000) Green.

33. C.I. B51810 Red 1 (45160) Red.

34-.-" C.I. Basic Yellow 19, C.I. Basic B1116 41 (1:1) Green.

N=N-N-NO1 01- 09 N 2 and OHZO om0H=-o11 ZnGh- (1:1 GB 1 C a EXAMPLE 35in. This solution is added to a solution of g. of sodium 3 grams (g.) ofC.I. Basic Blue 41, i.e. dyestufi of the formula v are pasted at roomtemperature with 5 g. of 80%-acetic acid. Then 250 milliliters (m1) ofhot water are poured sulfate and 2 g. of an adduct, quaternized withdimethyl sulfate, of mols of ethylene oxide and 2 mols of styrene oxideto N-octadecyl diethylene-triamine in 1250 ml. of water. After heatingthe liquor thus obtained to 60, a polyacrylonitrile fabric containingabout 15% of dyesites-atfording copolymer, e.g. a Dralon fabric, isintroduced. The liquor is heated within 10 minutes to 80 and then at arate of half a degree per minute up to 98". It is maintained at thistemperature for 2 hours, whereupon it is allowed to cool within minutesto The fabric; dyed in this way is rinsed several times in 40-warm Waterand in cold water, then treated with an aqueous solution of 4 g./literof an antistatic cationactive fatty acid imidazoline derivative, andfinally dried.

A level, deeply blue dyeing is obtained.

We claim:

1. A process for the production of level dyeings on copolymericacrylonitrile fibers having dyesites corresponding to a color saturationvalue above 2, comprising dyeing this material with an acid dye liquorwhich contains at least one basic dyestuff and, as dye assistant, apolyamine the molecule of which consists of a polyalkene polyaminemoiety having from three to five quaternized basic nitrogen atoms, apolyglycol ether chain of from 10 to 50 ethyleneoxy groups and at leastone lipophilic substitucnt, and steaming and rinsing the resultingdyeing.

2. A process according to claim 1, wherein the dye assistant is apermethylated N-octadecyl-diethylene triamine which contains apolyglycol ether chain having to ethyleneoxy groups.

3. A process as defined in claim 1, wherein the pH of the dye liquor iswithin the range between 3.5 and 5.

4. An acid dye liquor for use in the production of level dyeings oncopolymeric acrylonitrile fibers having dyesites corresponding to acolor saturation value above 2, said acid dye liquor containing at leastone basic dyestuif for coloring said fibers and, as dye assistant, apolyamine the molecule of which consists of a polyalkene polyaminemoiety having from three to five quaternized basic nitrogen atoms, apolyglycol ether chain of from 10 to 50 ethyleneoxy groups and at leastone lipophilic substituent.

5. A dye liquor as defined in claim 4, wherein the pH of said liquor atintroduction of said fibers is within the range between 3.5 and 5.

6. A process as defined in claim 1, wherein said polyamine dye assistantis the condensation product of 15 to 20 equivalents of ethylene oxidewith N-octadecyl diethylenetriamine quaternized with dimethyl sulfate.

7. A process as defined in claim 1, wherein said polyamine dye assistantis the condensation product of 20 mols of ethylene oxide and 2 mols ofstyrene oxide With N-octadecyl diethylenetriamine, per mol of thelatter, quaternized with dimethyl sulfate.

8. A process as defined in claim 1, wherein said polyamine dye assistantis the condensation product of 15 to 20 mols of ethylene oxide and 1 molof propylene oxide with 1 mol of N-octadecyl-diethylenetriamine,quaternized with dimethyl sulfate.

9. A process as defined in claim 1, wherein said polyamine dye assistantis the condensation product of 20 mols of ethylene oxide with 1 mol ofN-octadecyl-diethylenetriamine, quaternized with dimethyl sulfate.

10. A process as defined in claim 1, wherein said polyamine dyeassistant is the condensation product of 12 mols of ethylene oxide with1 mol of N-oleyl-triethylenetetramine, quaternized with dimethylsulfate.

11. A process as defined in claim 1, wherein said polyamine dyeassistant is the condensation product of 15 mols of ethylene oxide with1 mol of N-hexadecyl-tetraethylenepentamine, quaternized with dimethylsulfate.

12. A process as defined in claim 1, wherein said polyamine dyeassistant is the condensation product of 15 to 20 mols of ethylene oxidewith 1 mol of N-octadecyldipropylenetriamine, quaternized with dimethylsulfate.

33. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 15 to 20 equivalents ofethylene oxide with N-octadecyl diethylenetriamine quaternized withdimethyl sulfate.

14. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 20 mols of ethylene oxide and 2mols of styrene oxide with N-octadecyl diethylenetriamine, per mol ofthe latter, quaternized with dimethyl sulfate.

15. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 15 to 20 mols of ethylene oxideand 1 mol of propylene oxide with 1 mol ofN-octadecyl-diethylenetriamine, quaternized with dimethyl sulfate.

16. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 20 mols of ethylene oxide with1 mol of N-octadecyldiethylenetriarnine, quaternized with dimethylsulfate.

17. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 12 mols of ethylene oxide with1 mol of N-oleyl-triethylenetetramine, quaternized with dimethylsulfate.

18. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 15 mols of ethylene oxide with1 mol of N-hexadecyltetraethylenepentamine, quaternized with dimethylsulfate.

19. A dye liquor according to claim 4, wherein said polyamine dyeassistant is the condensation product of 15 to 20 rnols of ethyleneoxide with 1 mol of N-octadecyl-dipropylenetriarnine, quaternized withdimethyl sulfate.

References (Jited UNITED STATES PATENTS 2,769,684 11/1956 Geigy et al884 X 2,891,835 6/1959 Matter et al. 855 2,967,755 1/1961 Keller 8-843,273,954 9/1966 Wachsmann et al. 884 X FOREIGN PATENTS 355,457 8/1961Switzerland.

NORMAN G. TORCHIN, Primary Examiner. J. TRAVIS BROWN, Examiner.

T. J. HERBERT, Assistant Examiner.

1. A PROCESS FOR THE PRODUCTION OF LEVEL DYEINGS ON COPOLYMERIC ACRYLONITRILE FIBERS HAVING DYESITES CORRESPONDING TO A COLOR SATURATION VALUE ABOVE 2, COMPRISING DYEING THIS MATERIAL WITH AN ACID DYE LIQUOR WHICH CONTAINS AT LEAST ONE BASIC DYESTUFF AND, AS DYE ASSISTANT, A POLYAMINE THE MOLECULE OF WHICH CONSISTS OF A POLYALKENE POLYAMINE MOIETY HAVING FROM THREE TO FIVE QUATERNIZED BASIC NITROGEN ATOMS, A POLYGLYCOL ETHER CHAIN OF FROM 10 TO 50 ETHYLENEOXY GROUPS AND AT LEAST ONE LIPOPHILIC SUBSTITUENT, AND STEAMING AND RINSING THE RESULTING DYEING. 